Hydroconversion process employing catalyst with specified pore size distribution

ABSTRACT

Heavy oils may be hydrotreated in the presence of a porous alumina support bearing metals of Group VIII and VI-B and optionally phosphorus, the catalyst having a Total Surface Area of 165-230 m 2  /g, a Total Pore Volume of 0.5-0.8 cc.g, and a Pore Diameter Distribution whereby less than about 5% of the Total Pore Volume is present as primary micropores of diameter less than 80Å, and secondary micropores of diameter of ±20Å of a Pore Mode of 100-135Å are present in amount of at least about 65% of the micropore volume having pores with diameter less than 250Å, and 22-29% of the Total Pore Volume is present as macropores of diameter &gt;250Å. The process of the instant invention is particularly effective in achieving desired levels of hydrodemetallation, hydrodesulfurization, and hydrocracking of asphaltenes in the fraction of hydrotreated/hydrocracked petroleum resid product having a boiling point greater than 1000° F.

FIELD OF THE INVENTION

This invention relates a process for hydrotreating a hydrocarbon feed.More particularly it relates to a hydroconverison process employingcatalyst with a specified pore size distribution.

BACKGROUND OF THE INVENTION

As is well known to those skilled in the art, it is desired to convertheavy hydrocarbons, such as those having a boiling point above about1000° F., into lighter hydrocarbons which are characterized by highereconomic value. It is also desirable to treat hydrocarbon feedstocks,particularly petroleum residues, to achieve other goals includinghydrodesulfurization (HDS), hydrodenitrification (HDN), carbon residuereduction (CRR), and hydrodemetallation (HDM)--the latter particularlyincluding removal of nickel compounds (HDNi) and vanadium compounds(HDV).

These processes typically employ hydrotreating catalysts with specifiedranges of pores having relatively small diameters (i.e. micropores,herein defined as pores having diameters less than 250 Å) and poreshaving relatively large diameters (i.e. macropores, herein defined aspores having diameters greater than 250 Å).

U.S. patent application Ser. No. 194,379 (Dai et al., filed May 13,1988) now U.S. Pat. No. 5,047,142 discloses a catalyst compositionuseful in the hydroprocessing of a sulfur- and metal-containingfeedstock comprising an oxide of nickel or cobalt and an oxide ofmolybdenum on a porous alumina support in such a manner that themolybdenum gradient of the catalyst has value of less than 6.0 and15-30% of the nickel or cobalt is in an acid extractable form, andhaving a surface area of 150-210 m² /g, a Total Pore Volume (TPV) of0.50-0.75 cc/g, and a pore size distribution such that less than 25% TPVis in pores having diameters of less than 100 Å, 70.0-85.0% TPV is inpores having diameters of 100Å-160 Åand 1.0-15.0% TPV is in pores havingdiameters of greater than 250 Å.

U.S. patent application Ser. No. 168,095 now Dai et al. U.S. Pat. No.4,941,964 (filed Mar. 14, 1988) discloses a process for thehydrotreatment of a sulfur- and metal-containing feed which comprisescontacting said feed with hydrogen and a catalyst in a manner such thatthe catalyst is maintained at isothermal conditions and is exposed to auniform quality of feed, the catalyst comprising an oxide of a GroupVIII metal, an oxide of a Group VI-B metal and 0-2.0 weight % of anoxide of phosphorus on a porous alumina support, and having a surfacearea of 150-210 m² /g and a Total Pore Volume (TPV) of 0.50-0.75 cc/gsuch that 70-85% TPV is in pores having diameters of 100Å-160 Å and5.5-22.0% TPV is in pores having diameters of greater than 250 Å.

Robinson et al. U.S. Pat. No. 4,738,944 discloses a catalyst compositionuseful in the hydrotreatment of hydrocarbon oils, the catalystcontaining nickel and phosphorus and about 19-21.5% Mo (calculated asthe oxide) on a porous refractory oxide, having a narrow pore sizedistribution wherein at least 10% TPV is in pores having diameters lessthan 70 Å, at least 75% TPV is in pores having diameters between 50-110Å, at least 60% TPV is in pores having diameters within about 20 Å aboveand below the average pore diameter; and at most 25% TPV, mostpreferably less than 10% TPV, is in pores having diameters greater than110 A.

Lindsley et al. U.S. Pat. No. 4,652,545 discloses a catalyst compositionuseful in the hydroconversion of heavy oils, the catalyst containing0.5-5% Ni or Co and 1.8-18% Mo (calculated as the oxides) on a porousalumina support, having 15-30% of the Ni or Co in an acid extractableform, and further characterized by having a Total Pore Volume (TPV) of0.5-1.5 cc/g with a pore diameter distribution such that (i) at least70% TPV is in pores having 80-120 Å diameters, (ii) less than 0.03 cc/gof TPV is in pores having diameters of less than 80 Å, and (iii)0.05-0.1 cc/g of TPV is in pores having diameters of greater than 120 Å.

Hensley, Jr. et al. U.S. Pat. No. 4,395,328 discloses a process for thehydroconversion of a hydrocarbon stream containing asphaltenes and asubstantial amount of metals, comprising contacting the stream (in thepresence of hydrogen) with a catalyst present in one or more fixed orebullating beds, the catalyst comprising at least one metal which may bea Group VI-B or Group VIII metal, an oxide of phosphorus, and an aluminasupport, where the alumina support material initially had at least 0.8cc/gm of TPV in pores having diameters of 0-1200 Å, and at least 0.1cc/gm of TPV is in pores having diameters of 1200-50,000 Å, and thesupport material was heated with steam to increase the average porediameter of the catalyst support material.

Tamm U.S. Pat. No. 4,341,625 discloses a process for hydrodesulfurizinga metal-containing hydrocarbon feedstock which comprises contacting thefeedstock with a catalyst comprising at least one hydrogenation agent(i.e. Group VI-B or Group VIII metal or combinations thereof) on aporous support, the catalyst being further characterized by having a TPVof 0.5-1.1 cc/g with at least 70% TPV in pores having diameters of80-150 Å and less than 3% TPV in pores having diameters greater than1000 Å.

Angevine et al. U.S. Pat. No. 4,328,127 discloses a catalyst compositionfor use in the hydrodemetallation-desulfurization of residual petroleumoils, the catalyst comprising a hydrogenating component (i.e. Group VI-Bor Group VIII metal, or combinations thereof) on a porous support, andbeing further characterized by having a TPV of 0.45-1.5 cc/g with 40-75%TPV in pores having diameters of 150-200 Å, and up to 5% TPV in poreshaving diameters of greater than 500 Å.

Sawyer U.S. Pat. No. 4,309,278 discloses a process for thehydroconversion of a hydrocarbon feedstock comprising contacting thefeedstock with hydrogen and a catalyst in a fixed bed, moving bed,ebullating bed, slurry, disperse phase, or fluidized bed reactor, wherethe catalyst comprises a hydrogenation component (i.e. Group VI-B orGroup VIII metal) on a porous support, and is further characterized byhaving a TPV of 1.0-2.5 cc/g with no more than 0.05-0.20 cc/g of TPV inpores having diameters of greater than 400 Å.

Hensley, Jr. et al. U.S. Pat. No. 4,305,965 discloses a process for thehydrotreatment of a hydrocarbon stream comprising contacting the streamwith hydrogen and a catalyst, the catalyst comprising chromium,molybdenum, and at least one Group VIII metal on a porous support, andfurther characterized by having a TPV of 0.4-0.8 cc/g with 0-50% TPV inpores having diameters smaller than 50Å, 30-80% TPV in pores havingdiameters of 50-100Å, 0-50% TPV in pores having diameters of 100-150 Å,and 0-20% TPV in pores having diameters greater than 150 Å.

Hensley, Jr. et al. U.S. Pat. No. 4,297,242 discloses a 2-stage processfor the catalytic hydrotreatment of hydrocarbon streams containing metaland sulfur compounds, the process comprising: (i) first contacting thefeedstock with hydrogen and a demetallation catalyst comprising a GroupVI-B and/or Group VIII metal; and (ii) thereafter reacting the effluentwith a catalyst consisting essentially of at least one Group VI-B metalon a porous support, and having a TPV of 0.4-0.9 cc/g and a pore sizedistribution such that pores having diameters of 50-80 Å constitute lessthan 40% TPV, pores having diameters of 80-100 Å constitute 15-65% TPV,pores having diameters of 100 130 Å constitute 10-50% TPV, and poreshaving diameters of greater than 130 Å less than 15% TPV.

Oleck et al. U.S. Pat. No. 4,089,774 discloses a process for thedemetallation and desulfurization of a hydrocarbon oil comprisingcontacting the oil with hydrogen and a catalyst, the catalyst comprisinga Group VI-B metal and an iron group metal (i.e. iron, cobalt, ornickel) on a porous support, and having a surface area of 125-210 m² /gand TPV of 0.4-0.65 cc/g with at least 10% TPV in pores having diametersless than 30 Å, at least 50% of pore volume accessible to mercury beingin pores having diameters of 30-150 Å, and at least 16.6% of poresaccessible to mercury being in pores having diameters greater than 300Å.

Rosinski et al. U.S. Pat. No. 4,082,695 discloses a catalyst for use inthe demetallation and desulfurization of petroleum oils, the catalystcomprising a hydrogenating component (i.e. cobalt and molybdenum) on aporous support, and having a surface area of 110-150 m² /g and a poresize distribution such that at least 60% a TPV is in pores havingdiameters of 100-200 Å and not less than 5% TPV is in pores havingdiameters greater than 500 Å.

Tamm U.S. Pat. No. 4,066,574 discloses a catalyst composition useful inthe hydrodesulfurization of a hydrocarbon feedstock containingorganometallic compounds, the catalyst comprising Group VI-B and GroupVIII metal components on a porous support, and having a TPV of 0.5-1.1cc/g with a pore diameter distribution such that at least 70% TPV is inpores of diameters of 80-150 Å and less than 3% TPV is in pores havingdiameters greater than 1000 Å.

Hamner U.S. Pat. No. 4,051,021 discloses a catalytic process for thehydrodesulfurization of a hydrocarbon feed which comprises contactingthe feed with hydrogen and a catalyst, the catalyst comprising a GroupVI-B and Group VIII metal on a porous support, and having a TPV of0.3-1.0 cc/g with a pore diameter distribution such that greater than50% TPV is in pores of diameters of 70-160 Å, and pores having diametersbelow 70 Å and above 160 Å are minimized.

Riley U.S. Pat. No. 4,048,060 discloses a two-stage process forhydrodesulfurizing a heavy hydrocarbon feed which comprises: (i)contacting the feed with hydrogen and a first catalyst to produce afirst hydrodesulfurized hydrocarbon product, the first catalystcomprising a Group VI-B and Group VIII metal on a porous support andhaving a mean pore diameter of 30-60 Å; and (ii) contacting the firsthydrodesulfurized hydrocarbon product with hydrogen and a secondcatalyst under hydrodesulfurization conditions, the second catalystcomprising a Group VI-B and Group VIII metal on a porous support andbeing further characterized by having a TPV of 0.45-1.50 cc/g with0.-0.5 cc/g of TPV in pores having diameters greater than 200 Å, 0-0.05cc/g of TPV in pores having diameters below 120 Å, and at least 75% TPVin pores having diameters ±10 Å of a mean pore diameter of 140-190 Å.

Rosinski et al. U.S. Pat. No. 3,876,523 discloses a process for thedemetallizing and desulfurizing of residual petroleum oil comprisingcontacting the oil with hydrogen and a catalyst, the catalyst comprisinga Group VI-B and Group VIII metal on a porous support and having a poresize distribution such that greater than 60% TPV is in pores havingdiameters of 100-200 Å, at least 5% TPV is in pores having diametersgreater than 500 Å, and 10% TPV or less is in pores having diametersless than 40 Å, and the surface area of the catalyst is 40-150 m² /g.

Riley et al. U.S. Pat. No. 3,770,617 discloses a process for thedesulfurization of a petroleum hydrocarbon feed comprising contactingthe feed with hydrogen and a catalyst, the catalyst comprising a GroupVI-B or Group VIII metal on a porous support and having greater than 50%TPV in pores of 30-80 Å, less than 4% TPV in pores having diameters200-2000 Å, and at least 3% TPV in pores having diameters greater than2000 Å.

Riley et al. U.S. Pat. No. 3,692,698 discloses a catalyst useful inhydroprocessing of heavy feed stocks, the catalyst comprising a mixtureof Group VI-B and Group VIII metals on a porous support and having apore size distribution such that a major portion of its TPV is in poresof diameters ranging from 30-80 Å, less than 4% TPV is in pores ofdiameters of 200-2000 Å, and at least 3% TPV is in pores of diametersgreater than 2000 Å.

Early petroleum distillate hydrotreating catalysts generally weremonomodal catalysts with very small micropore diameters (less than say100 Å) and rather broad pore size distributions. First generationpetroleum resid hydro-treating catalysts were developed by introducing alarge amount of macroporosity into a distillate hydrotreating catalystpore structure to overcome the diffusion resistance of large molecules.Such catalysts, which are considered fully bimodal HDS/HDM catalysts,are typified by U.S. Pat. No. 4,395,328 and 4,089,774 supra.

Another approach to developing improved catalysts for petroleum residprocessing has involved enlarging the micropore diameters of essentiallymonomodal catalysts (having no significant macroporosities) to overcomethe above described diffusion limitations. Essentially monomodalcatalysts with small micropore diameters and low macroporositiesdesigned for improved petroleum resid HDS include those disclosed inU.S. Pat. Nos. 4,738,944; 4,652,545; 4,341,625; 4,309,378; 4,306,965;4,297,242; 4,066,574; 4,051,021; 4,048,060 (1st stage catalyst);3,770,617; and 3,692,698, supra. Essentially monomodal catalysts withlarger micropore diameters and low macroporosities designed for improvedpetroleum resid HDM include those disclosed in U.S. Pat. No. 4,328,127;4,309,278; 4,082,695; 4,048,060 (2nd stage catalyst); and 3,876,523,supra.

A recent approach to developing improved catalysts for petroleum residprocessing has involved the use of catalysts having micropore diametersintermediate between the above described monomodal HDS and HDMcatalysts, as well as sufficient macroporosities so as to overcome thediffusion limitations for petroleum bottoms HDS (i.e., sulfur removalfrom hydrocarbon product of a hydrotreated petroleum resid having aboiling point greater than 1000° F.) but limited macroporosities tolimit poisoning of the interiors of the catalyst particles. Catalysts,with micropore diameters intermediate between the above-describedmonomodal HDS and HDM catalysts with limited macroporosities includethose of U.S. patent application Ser. No. 168,095 (now U.S. Pat. No.4,941,964); and 194,378 (now U.S. Pat. No. 5,047,142) supra.

However, none of the above-identified catalyst types has been found tobe effective for achieving desired levels of hydroconverison offeedstocks components having a boiling point greater than 1000° F. toproducts having a boiling point less than 1000° F. while simultaneouslyyielding a 1000° F.+product having a lower sulfur content.

It is an object of this invention to provide a process for hydrotreatinga charge hydrocarbon feed. Other objects will be apparent to thoseskilled in the art.

STATEMENT OF THE INVENTION

In accordance with certain of its aspects, this invention is directed toa process for hydrotreating a charge hydrocarbon feed containingcomponents boiling above 1000° F., sulfur, metals, and asphaltenes whichcomprises

contacting said charge hydrocarbon feed with hydrogen at isothermalhydrotreating conditions in the presence of, as catalyst, a porousalumina support bearing 3-6 w % of a Group VIII metal oxide, 14.5-24 w %of a Group VI-B metal oxide, and 0-6 w % of a phosphorous oxide, saidcatalyst having a Total Surface Area of 165-230 m² /g, a Total PoreVolume TPV of 0.5-0.8 cc/g, and a Pore Diameter Distribution wherebyless than about 5% of the Total Volume Pore is present as primarymicropores of diameter less than about 80 Å and secondary micropores ofdiameter ±20 Å of a Pore Mode of about 100-135 Å are present in amountof at least about 65% of the micropore volume having pores with diameterless than 250 Å, and about 22-29% of the Total Pore Volume is present asmacropores of diameter ≧250 Å thereby forming hydrotreated productcontaining decreased contents of components boiling above 1000° F.,sulfur, metals, and asphaltenes; and

recovering said hydrotreated product containing decreased contents ofcomponents boiling about 1000° F., sulfur, metals and asphaltenes.

DESCRIPTION OF THE INVENTION

The charge hydrocarbon feed which may be charged to the process of thisinvention may include heavy, high boiling petroleum cuts typified by gasoils, vacuum gas oils, petroleum cokes, residual oils, vacuum resid,etc. The process of this invention is particularly useful to treat highboiling oils which contain components boiling above 1000° F. to convertthem to products boiling below 1000° F. The charge may be a petroleumfraction having a boiling point of above 650° F. characterized bypresence of an undesirably high content of components boiling above1000° F., metals, sulfur, and asphaltenes.

It is a particular feature of the process of this invention that it maypermit treating of hydrocarbon charge, particularly those containingcomponents boiling above about 1000° F., to form product which ischaracterized by an increased content of components boiling below 1000°F. and by decreased content of undesirable components typified bymetals, sulfur, and asphaltenes (herein defined as the quantity ofn-heptane-insolubles minus the quantity of toluene-insolubles in thefeedstock or product).

A typical charge which may be utilized is an Arabian Medium/Heavy VacuumResid having the following properties:

                  TABLE                                                           ______________________________________                                        Property           Value                                                      ______________________________________                                        API Gravity         4.8                                                       1000° F.+, vol %                                                                          87.5                                                       1000° F.+, w %                                                                            88.5                                                       1000° F.- w %                                                                             11.5                                                       Sulfur, w %         5.0                                                       Total Nitrogen, wppm                                                                             4480                                                       Hydrogen, w %       10.27                                                     Carbon, w %         84.26                                                     Alcor MCR, w %     22.2                                                       Kinematic Viscosity, cSt                                                      @ 212 F.           2430                                                       @ 250 F.           410                                                        @ 300 F.           117                                                        Pour Point, °F.                                                                           110                                                        n-C.sub.5 Insolubles, w %                                                                        28.4                                                       n-C.sub.7 Insolubles, w %                                                                         9.96                                                      Toluene Insolubles, w %                                                                           0.02                                                      Asphaltenes, w %    9.94                                                      Metals, wppm                                                                  Ni                 49                                                         V                  134                                                        Fe                 10                                                         Cu                 3                                                          Na                 49                                                         Total Metals wppm  245                                                        Chloride, wppm     28                                                         ______________________________________                                    

In practice of the process of this invention, the charge hydrocarbonfeed is contacted with hydrogen at isothermal hydrotreating conditionsin the presence of catalyst. Hydrogen is charged at a rate of2000-10,000 SCFB, preferably 3000-8000, say 7000 SCFB. Temperature ofoperation is typically 650° F.-850° F., preferably 700° F.-800° F., say770° F. The operation is essentially isothermal; and the temperature maytypically vary throughout the bed by less than about 20° F. Pressure ofoperation may be 1500-3500 psig, preferably 1800-2500 psig, say 2250psig.

The catalyst support may be alumina. Although the alumina may be alpha,beta, theta, or gamma alumina, it is preferred to utilize gamma alumina.

The alumina substrate which may be employed yields a finished catalystwhich is characterized by Total Surface Area, Total Pore Volume, andPore Diameter Distribution. The Total Surface Area is 165-230,preferably 195-215, say 209 m² /g. The Total Pore Volume may be 0.5-0.8,preferably 0.73-0.8, say 0.77 cc/g.

The Pore Diameter Distribution is such that less than 5%, preferably0-3% say 19% of the Total Pore Volume is present as primary microporesof diameter of less than about 80 Å.

Secondary micropores of pore diameter which is ±20 Å of a pore mode of100Å-135 Å, preferably 105Å-125 Å, say about 105 Å, are present inamount of ≧65% preferably 65-70% say 68% of micropore volume havingpores with diameter less than 250 Å.

Macropores of diameter of greater than about 250 Å are present in amountof about 22-29%, preferably 25%-29%, say 26% of the Total Pore Volume.

It should be noted that the Pore Size Distribution in the finishedcatalyst and particularly the percentage of the secondary microporespores of diameter 100-135 A in the finished catalyst are essentially thesame as in the charge alumina from which it is prepared. The TotalSurface Area, the Total Pore Volume, and the Pore Volume of the finishedcatalyst may be 90%-100%, say 97% of the charge alumina from which it isprepared.

The alumina charge may be loaded with metals to yield a product catalystcontaining a Group VIII oxide in amount of 3-6 w %, preferably 3-3.5 w%, say 3.2 w %, a Group VI-B metal oxide in amount of 14.5-24,preferably 14.5-16.5 w %, say 15.2 w % and a phosphorous oxide (P₂ O₅)in amount of 0-6 w %, preferably 0-0.2, say ≦0.2 w %.

The Group VIII metal may be a non-noble metal such as iron, cobalt, ornickel, or a noble metal such as ruthenium, rhodium, palladium, osmium,iridium, or platinum. This metal may be loaded onto the aluminatypically from a 10%-50%, say 30% aqueous solution of a water-solublesalt (e.g. a nitrate, acetate, oxalate etc.). The preferred metal may benickel, employed as a 30 w % aqueous solution of nickel nitrate.

The Group VI-B metal may preferably be chromium, molybdenum, ortungsten. This metal may be loaded onto the alumina typically from a10%-25%, say 15% aqueous solution of a water-soluble salt such asammonium molybdate.

The phosphorus component, when employed, may be employed as a 20%-90%say 85 w % aqueous solution of phosphoric acid H₃ PO₄.

These catalyst metals (and phosphorus when present) may be loaded ontothe alumina support by immersing the latter in a solution of the former.Although it is preferred to load the metals and phosphorussimultaneously, it is possible to load each separately. When phosphorusis not present, small amounts of H₂ O₂ may be added to stabilize theimpregnating solution. Loading of each metal may be effected byimmersing the alumina support in the aqueous solution for 12-36 hours,say 24 hours at 60° F.-100° F., say 80° F. followed by draining, dryingat 220° F.-300 ° F., say 250° F. for 2-10 hours, say 4 hours, andcalcining at 900° F.-1200° F., say 1095° F. for 0.5-5 hours, say 0.5hour.

The charge alumina may preferably be formed into desired shape bycasting or extrusion. Preferably the catalyst may be extruded to formcylinders of diameter by 0.035 inch-0.041 inch, say 0.038 inch andlength of 0.1-0.5 inch, say 0.15 inch.

In practice of the process of this invention, the catalyst, preferablyin the form of extruded cylinders of 0.038 inch diameter and 0.15 inchlength may be placed within a reactor. The particle size distributionmay be; <0.5 mm-0.5 w % max; <5.0 mm 5 w % max; <1.6 mm 10 w % max; <2.5mm 40 w % max; and >15 mm 10 w % max. The hydrocarbon charge is admittedto the lower portion of the bed in liquid phase at 650° F.-800° F.,preferably 700° F.-800° F., say 770° F. and 1500-3500 psig, preferably2000-3000 psig, say 2250 psig. Hydrogen gas is admitted with thehydrocarbon charge in amount of 3000-10,000 SCFB, preferably 5000-8000SCFB, say 7000 SCFB. The hydrocarbon charge passes through the bed at aLHSV of 0.1-3, preferably 0.3-1, say 0.56. During operation, the bedexpands to form an ebullated bed with a defined upper level. Operationis essentially isothermal with a typical maximum temperature differencebetween the inlet and the outlet of 0° F.-50° F., preferably 0° F.-30°F., say 15° F.

In a less preferred embodiment, the reaction may be carried out in oneor more continuously stirred tank reactors (CSTR) which also providesessentially isothermal conditions.

During passage through the reactor, preferably containing an ebullatedbed, the hydrocarbon feedstock may be converted to lower boilingproducts by the hydrotreating reaction. In a typical embodiment, acharge containing 60 w %-95%, say 89 w % boiling above 1000° F. and 0 w%-30 w %, say 12 w % boiling in the 600° F.-1000° F. range may beconverted to a hydrotreated product containing only 35 w %-65 w %, say58 w % boiling above 1000° F. The sulfur of the original charge istypically 5.0 w %; the sulfur content of the unconverted 1000°F.+component in the product is typically 3.1 w %.

ADVANTAGES OF THE INVENTION

It will be apparent to those skilled in the art that this invention ischaracterized by advantages including the following:

(i) it permits attainment of yield of hydrocarbon products boiling below1000° F.;

(ii) it permits operation to yield highly desulfurized hydrocarbonproduct;

(iii) it permits operation to yield hydrocarbon product characterized bylower content of metals;

(iv) the 650° F.-1000° F. portion of the product is also characterizedby a desirably lower content of nitrogen and sulfur;

(v) the 1000° F.+component of the product is characterized by asignificantly lower content of sulfur;

(vi) the 1000F.+component of the product is characterized by asignificantly lower content of asphaltenes;

(vii) the total liquid product is characterized by a low content ofasphaltenes. Thus it would be expected to improve unit operability andto prevent unscheduled shutdowns caused by sediment deposition in thedown-stream fractionation equipment.

Practice of the process of this invention will be apparent to thoseskilled in the art from the following wherein all parts are parts byweight unless otherwise stated. Control examples are designated by anasterisk.

DESCRIPTION OF SPECIFIC EMBODIMENTS EXAMPLE I

In this example which represents the best mode presently known ofcarrying out the process of this invention, the charge hydrocarbon isthe Arabian Medium/Heavy Vacuum Resid having the properties set forth inthe table supra. It should be noted that this charge hydrocarbon isparticularly characterized by the presence of 87.5 v % of componentshaving a boiling point above 1000° F., by a sulfur content of 5 w %, andby a total metals content of 245 wppm.

The catalyst is prepared from a commercially available gamma aluminahaving the properties set forth in the Table which follows which notesthe Total Surface Area TSA in square meters per gram of alumina, TotalPore Volume TPV in cubic centimeters per gram, and the Pore Volume PV,as a percent of TPV, arising from pores of noted diameter (A):

                  TABLE                                                           ______________________________________                                                          Finished Charge                                             Property          Catalyst Alumina                                            ______________________________________                                        TSA m.sup.2 /g    197      224                                                TPV cc/g             0.78     0.99                                            PV % < 100Å   15       19                                                 PV % 100A-160Å                                                                              53       48                                                 PV % < 160Å   68       67                                                 PV % > 160Å   32       33                                                 PV % > 250Å   26       26                                                 PV % 500Å-10,000                                                                            22       22                                                 ______________________________________                                    

This alumina (780g) in the form of extrudate of diameter of 0.035-0.041inch is impregnated at 80° F. with 820 ml aqueous solution whichcontains 122 g of nickel nitrate hexahydrate and 185 g of ammoniummolybdate and 40 ml of hydrogen peroxide. The catalyst is dried at 250°F. for 4 hours and calcined at 1095° F. for 30 minutes.

The product catalyst is characterized as follows:

                  TABLE                                                           ______________________________________                                               Component                                                                             W %                                                            ______________________________________                                               MoO.sub.3                                                                              15.2                                                                 NiO      3.2                                                                  SiO.sub.2                                                                             ≦2.5                                                           SO.sub.4                                                                              ≦0.8                                                           Na.sub.2 O                                                                            ≦0.1                                                           P.sub.2 O.sub.5                                                                       <0.2                                                           ______________________________________                                    

It is also characterized by essentially the same Total Pore Volume,Total surface Area, and Pore Size Distribution percentages as is thecharge alumina (note Table supra)--but the Total Surface Area and theTotal Pore Volume may decrease somewhat.

The catalyst (100 parts) is in the form cylinders of 0.038 inch diameterand 0.15 inch length. The catalyst is dried at 80° F. for 24 hoursfollowed by calcining at 1010° F. for 1 hour. This catalyst is placedwithin the reaction vessel in which an ebullated bed is to bemaintained.

Charge hydrocarbon is admitted in liquid phase at 770° F. and 2250 psigto the ebullated bed at a space velocity LHSV of 0.56. Hydrogen isadmitted in amount of 7000 SCFB.

Product is collected and analyzed to yield the following data:

                  TABLE                                                           ______________________________________                                        Property                Value                                                 ______________________________________                                        % Sulfur Removal        63                                                    % Carbon Residue Reduction                                                                            45                                                    % Ni Removal            54                                                    % V Removal             75                                                    % S In Unconverted 1000° F.+ Fraction                                                            3.0                                                 % S In 650° F.-1000° F. Fraction                                                           1.05                                               % Hydroconversion of 1000° F.+                                                                   40.2                                                to 1000° F. - Materials                                                % N In 650° F.-1000° F. Fraction                                                           0.22                                               ______________________________________                                    

Upon distillation to recover (i) a first cut from the initial boilingpoint to 650° F., (ii) a second cut from 650° F. to 1000° F., and (iii)a third cut above 1000° F., the following is noted:

                  TABLE                                                           ______________________________________                                        EXAMPLE I                                                                                     Product                                                       ______________________________________                                        Cut 1: up to 650° F.                                                   Sp.Gr.            0.85                                                        Sulfur w %        0.25                                                        Cut 2: 650° F.-1000° F.                                         Sp.Gr.            0.93                                                        Sulfur w %        1.05                                                        Total N wppm      2242                                                        Basic N wppm      812                                                         Cut 3: 1000° F.+                                                       Sp.Gr.            1.03                                                        Sulfur w %        3.07                                                        ______________________________________                                    

From the above Table, it is apparent that the process of this inventionpermits increasing the conversion of the materials boiling below 1000°F. up to 40.2 w %. The Sulfur content of the 1000° F.+fraction isdecreased (from 5.0 w % in the feed) down to 3.1 w %. The metals contentis decreased (from 245 wppm) down to 85 wppm.

The process of this invention typically shows an Asphaltene CrackingAdvantage (when measured against the prior art commercial controlcatalyst of Example VII) of 8.5. The asphaltene content of the 1000F.+component of the product obtained by using this invention catalyst is10.36 w % relative to 11.95 wt % for the prior art commercial controlcatalyst.

The process of this invention typically shows a HydrodemetallationAdvantage (when measured against the prior art commercial controlcatalyst of Example VII) of 8.5. The Hydrodemetallation (HDV) Advantageis calculated as the weight % HDV measured for a particular example (X)minus the weight % HDV of a Standard (Y), this difference being dividedby the weight % HDV of the Standard.

The asphaltene content of the 1000° F. component of the product obtainedby using this invention is 10.36 w %. A typical prior art controlcatalyst yields 11.95 w % asphaltenes.

EXAMPLE II-VII*

In experimental Example II-III, the catalyst is prepared as in Example Iexcept that it contains different amounts of catalytic metals, differentTPV, TSA, and Pore Size Distribution--all as set forth in the Tablewhich follows. Also included are control Examples IV*-VII*. ControlExample V* utilizes a commercially available NiMo catalyst (the HDS-1443B brand of catalyst marketed by Criterion Catalyst Co.).

    __________________________________________________________________________    CATALYST PROPERTIES                                                                      I    II   III  VII* IV*  V*   VI*                                  Chem. Com. (wt. %):                                                                      NiMo NiMo NiMo NiMo NiMoP                                                                              NiMo NiMoP                                __________________________________________________________________________    MoO.sub.3  14.5-16.5                                                                          14.5-16.5                                                                          14.5-16.5                                                                          11.5-14.5                                                                          14.5-15.5                                                                          14.5-15.5                                                                          14.5-16.5                            NiO        3.0-3.5                                                                            3.0-3.5                                                                            3.0-35                                                                             3.2-4.0                                                                            3.0-3.5                                                                            3.0-35                                                                             3.0-35                               CoO        None None None None None None None                                 SiO.sub.2  ≦2.5                                                                        ≦2.5                                                                        ≦2.5                                                                        ≦1.0                                                                        ≦2.5                                                                        ≦2.5                                                                        ≦2.5                          SO.sub.4   ≦0.8                                                                        ≦0.8                                                                        ≦0.8                                                                        ≦0.8                                                                        ≦0.8                                                                        ≦0.8                                                                        ≦0.8                          Na.sub.2 O ≦0.1                                                                        ≦0.1                                                                        ≦0.1                                                                        ≦0.05                                                                       ≦0.1                                                                        ≦0.1                                                                        ≦0.1                          P.sub.2 O.sub.5                                                                          ≦0.2                                                                        ≦0.2                                                                        ≦0.2                                                                        ≦0.2                                                                        1.5-1.9                                                                            ≦0.2                                                                        1.6                                  Surface Area                                                                             209  190  170  314  182  194  269                                  (m.sup.2 /g)                                                                  TPV (cc/g)*                                                                              0.77 0.79 0.80 0.74 0.69 0.64 0.71                                 PV < 80Å (% TPV)*                                                                    1.9  0.7  0.3  53.3 2.1  1.3  33.9                                 Median PD  122  135  146  73   130  126  89                                   by Vol., Å*                                                               Micropore Mode                                                                           105  121  131  50   121  116  80                                   (dV/dD).sub.MAX), Å*                                                      PV dV/dD.sub.MAX ± 20A                                                                68.1 67.8 66.3 72.2 68.9 65.2 70.2                                 (% PV < 250Å)*                                                            PV > 250Å (% TPV)*                                                                   25.9 27.8 28.1 34.1 15.5 7.3  15.8                                 PV > 160Å (% TPV)*                                                                   32.3 36.2 40.1 37.4 23.2 16.3 20.6                                 PV 500A-10,000A                                                                          21.8 23.3 22.9 29   10.2 3.5  11.3                                 (% TPV)*                                                                      __________________________________________________________________________     *Pore Structure information determined using Micromeretics Autopore 9220      mercury porosimetry instrument.                                          

                  TABLE                                                           ______________________________________                                        Average Advantage for Hydrodemetallation (%)                                  (from 0.1 to 3.0 Barrels per Pound Catalyst Age)                              Catalyst         HDV*     HDNi**                                              ______________________________________                                        Example I        +2.2     +9.5                                                Example VII*     Base = 0 Base = 0                                            Example IV*      -5.0     +3.6                                                Example V*       -4.2     +6.7                                                Example VI*      -10.3    -3.2                                                ______________________________________                                         ##STR1##                                                                      ##STR2##                                                                 

From the above Table, it is apparent that the process of this inventionshows higher levels of vanadium and nickel removal than the controlexamples.

                                      TABLE                                       __________________________________________________________________________    Average Catalytic Activities (Wt. %)                                          (from 0.1 to 3.0 Barrels per Pound Catalyst Age)                                               Catalyst                                                                      Example I                                                                           Example VII*                                                                          Example IV*                                                                          Example V*                                                                           Example VI*                      __________________________________________________________________________    % Sulfur Removal 62.8  57.7    63.8   67.3   64.0                             % Carbon Residue Reduction*                                                                    45.0  40.0    45.8   48.0   49.0                             % Nickel Removal 54.1  49.4    51.2   52.7   47.8                             % Vanadium Removal                                                                             75.4  73.8    70.1   70.7   66.2                             % Hydroconversion of 1000° F.+                                                          40.2  41.2    41.0   41.6   44.9                             to 1000° F.- Materials**                                               % Hydroconversion Advantage***                                                                 -2.5  Base = 0                                                                              -0.5   +1.0   +9.0                             __________________________________________________________________________     *As measured with an Alcor microcarbon residue tester.                        **Average from 0.1 to approximately 4.0 barrels per pound catalyst age.       ##STR3##                                                                 

The Hydrodemetallation Advantage calculated for Examples I, IV, V andVII* is:

                  TABLE                                                           ______________________________________                                                    Hydrodemetallation Advantage                                      Example       HDV         HDNi                                                ______________________________________                                        I             +2.2        +9.4                                                IV*           -5.0        +3.6                                                V*            -4.2        +6.7                                                VI*           -10.3       -3.2                                                VII* (Control)                                                                              0           0                                                   ______________________________________                                    

The Average Catalytic Activity in weight % is determined over the agerange of 0.1-3.0 barrels per pound.

                  TABLE                                                           ______________________________________                                                   Example                                                            Property     I       IV*     V*    VI*   VII*                                 ______________________________________                                        % S Removal  63      64      67    64     58%                                 Carbon Residue                                                                             45      46      48    49    40                                   Reduction                                                                     % Ni Removal 54      51      53    48    49                                   % V Removal  75      70      71    66    74                                   % Hydro-       40.2  41        41.6                                                                                44.9                                                                                41.2                               converion °F.                                                          1000° F.+ to 1000° F.                                           Materials                                                                     Hydroconversion                                                                             -2.5    -0.5     1.0  +9.0  0                                   Advantage                                                                     ______________________________________                                    

                                      TABLE                                       __________________________________________________________________________    Average Product Quality Parameters                                            (from 0.1 to Approximately 4.0 Barrels per Pound Catalyst Age)                              Catalyst                                                                      Example I                                                                           Example VII*                                                                          Example IV*                                                                          Example V*                                                                           Example VI*                         __________________________________________________________________________    Initial Boiling Point - 650° F.                                        Specific Gravity (g/cc)                                                                     0.85  0.85    0.85   0.85   0.85                                Sulfur (Wt. %)                                                                              0.25  0.34    0.25   0.18   0.23                                650° F.-1000° F.                                                Specific Gravity (g/cc)                                                                     0.93  0.94    0.93   0.93   0.93                                Sulfur (Wt. %)                                                                              1.05  1.26    0.94   0.73   0.80                                1000° F.+                                                              Specific Gravity (g/cc)                                                                     1.03  1.04    1.03   1.03   1.03                                Sulfur (Wt. %)                                                                              3.07  3.42    3.11   2.86   3.32                                Asphaltenes (Wt. %)                                                                         10.4  12.0    12.0   11.4   14.0                                __________________________________________________________________________

From the above Tables, the following conclusions may be drawn:

(i) The catalysts of Examples I-II of this invention permit attainmentof desirable results when used in hydrodesulfurization and asphalteneconversion;

(ii) the process of the instant invention permits a high level ofdenickelization (HDNi) of the charge;

(iii) the process of the instant invention permits a high level ofasphaltene cracking conversion.

(iv) the process of the instant invention permits a high level of hydrodemetallation (HDM) of the charge;

(v) the process of the instant invention permits a high level of carbonresidue reduction (CCR); and

(vi) the process of the instant invention permits conversion offeedstock components having a boiling point above about 1000° F. toproduct components having a boiling point less than 1000° F.;

Although this invention has been illustrated by reference to specificembodiments, it will be apparent to those skilled in the art thatvarious charges and modifications may be made which clearly fall withinthe scope of the invention.

We claim:
 1. A process for hydrotreating a charge hydrocarbon fuelcontaining components boiling above 1000° F., and sulfur, metals, andasphaltenes which comprisescontacting said charge hydrocarbon feed withhydrogen at isothermal hydrotreating conditions in the presence of, ascatalyst, a porous alumina support bearing 3.0-3.5% NiO, 14.5-16.5%MoO₃, and <0.2 w % of P₂ O₅, said catalyst having a Total Surface Areaof 165-230 m² /g, a Total Pore Volume of 0.73-0.8 cc/g, and a PoreDiameter Distribution whereby 0-3% of the Total Pore Volume is presentas primary micropores of diameter less than about 80 Å, and secondarymicropores having diameters ±20 Å of a Pore Mode of 105-125 Å arepresent in amount of at least about 65% of the micropore volume havingpores with diameter less than 250 Å, and 25-29% of the Total Pore Volumeis present as macropores of diameter greater than about 250 Å, therebyforming hydrotreated product containing decreased contents of componentsboiling above 1000° F., sulfur, metals, and asphaltenes; and recoveringsaid hydrotreated product containing decreased contents of componentsboiling above 1000° F., sulfur, metals, and asphaltenes.
 2. A processfor hydroconversion of a charge hydrocarbon feed of boiling pointgreater than 1000° F. to form product having a boiling point less than1000° F. which comprisescontacting said charge hydrocarbon feed withhydrogen at isothermal hydrotreating conditions in the presence of, ascatalyst, a porous support bearing 3.0-3.5 w % of a Group VIII metaloxide, 14.5-16.5 w % of a Group VI-B metal oxide, and less than 0.2 w %of a phosphorus oxide, said catalyst having a Total Surface Area of195-215 m² /g, a Total Pore Volume of 0.73-0.8 cc/g, and a Pore DiameterDistribution whereby less than 3% of the Total Pore Volume is present asprimary micropores of diameter ≦80 Å, and secondary micropores ofdiameters ±20 Å of a pore mode of 100-135 Å are present in amount of atleast about 65% of the micropore volume having pores with diameter lessthan 250 Å, and 25-29% of the Total Pore Volume is present as macroporesof diameter ≧250 Å, thereby forming hydrotreated product containingincreased content of product having a boiling point less than 1000° F.;and recovering said hydrotreated product containing increased content ofproduct having a boiling point less than 1000° F.
 3. A process asclaimed in claim 2 wherein said Group VIII metal oxide is present inamount of about 3.2 w %.
 4. A process as claimed in claim 2 wherein saidGroup VI-B metal is present in amount of about 15 w % as an oxide.
 5. Aprocess as claimed in claim 2 wherein said porous support is alumina.